scholarly journals Multiwavelets Applied to Metal-Ligand Interactions: Energies Free from Basis Set Errors

2021 ◽  
Author(s):  
Anders Brakestad ◽  
Peter Wind ◽  
Stig Rune Jensen ◽  
Luca Frediani ◽  
Kathrin Hopmann
Keyword(s):  
Transition Metal ◽  
Basis Set ◽  
Basis Sets ◽  
Electronic Interaction ◽  
Promising Alternative ◽  
Ligand Interactions ◽  
Counterpoise Corrections ◽  
Solvent Molecules ◽  
Catalyzed Reactions ◽  
Metal Ligand

The following article will be submitted to the Journal of Chemical Physics. It is thus not a peer-reviewed manuscript. After it is hopefully accepted for publication, it will be found (in revised form) at https://aip.scitation.org/journal/jcp<div><br></div><div>Transition metal-catalyzed reactions invariably include steps, where ligands associate or dissociate. In order to obtain reliable energies for such reactions, sufficiently large basis sets need to be employed. In this paper, we have used high-precision Multiwavelet calculations to compute the metal-ligand association energies for 27 transition metal complexes with common ligands such as H2, CO, olefins and solvent molecules. By comparing our Multiwavelet results to a variety of frequently used Gaussian-type basis sets, we show that counterpoise corrections, which are widely employed to correct for basis set superposition errors, often lead to underbinding. Additionally, counterpoise corrections are difficult to employ, when the association step also involves a chemical transformation. Multiwavelets, which can be conveniently applied to all types of reactions, provide a promising alternative for computing electronic interaction energies free from any basis set errors. <br></div>

scholarly journals Multiwavelets Applied to Metal-Ligand Interactions: Energies Free from Basis Set Errors

2021 ◽  
Author(s):  
Anders Brakestad ◽  
Peter Wind ◽  
Stig Rune Jensen ◽  
Luca Frediani ◽  
Kathrin Hopmann
Keyword(s):  
Transition Metal ◽  
Basis Set ◽  
Basis Sets ◽  
Electronic Interaction ◽  
Promising Alternative ◽  
Ligand Interactions ◽  
Counterpoise Corrections ◽  
Solvent Molecules ◽  
Catalyzed Reactions ◽  
Metal Ligand

The following article will be submitted to the Journal of Chemical Physics. It is thus not a peer-reviewed manuscript. After it is hopefully accepted for publication, it will be found (in revised form) at https://aip.scitation.org/journal/jcp<div><br></div><div>Transition metal-catalyzed reactions invariably include steps, where ligands associate or dissociate. In order to obtain reliable energies for such reactions, sufficiently large basis sets need to be employed. In this paper, we have used high-precision Multiwavelet calculations to compute the metal-ligand association energies for 27 transition metal complexes with common ligands such as H2, CO, olefins and solvent molecules. By comparing our Multiwavelet results to a variety of frequently used Gaussian-type basis sets, we show that counterpoise corrections, which are widely employed to correct for basis set superposition errors, often lead to underbinding. Additionally, counterpoise corrections are difficult to employ, when the association step also involves a chemical transformation. Multiwavelets, which can be conveniently applied to all types of reactions, provide a promising alternative for computing electronic interaction energies free from any basis set errors. <br></div>

Syntheses of Chelating Tetrazole-Containing Ligands and Studies of Their Palladium(II) and Ruthenium(II) Complexes

1995 ◽  
Vol 48 (9) ◽  
pp. 1625 ◽  
Author(s):  
AJ Downard ◽  
PJ Steel ◽  
J Steenwijk
Keyword(s):  
Cyclic Voltammetry ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Absorption Spectroscopy ◽  
Electronic Absorption ◽  
Ph Control ◽  
Strong Electron ◽  
Ligand Interactions ◽  
Metal Ligand

Eleven chelating tetrazole -containing ligands have been synthesized, and their complexes with palladium(II) and ruthenium(II) prepared. Proton n.m.r. spectroscopy, electronic absorption spectroscopy and cyclic voltammetry have been used to study the nature of the metal-ligand interactions in these complexes. The negatively charged tetrazolate group is shown to be a strong electron donor with very different properties to those of the protonated or alkylated tetrazole group. This leads to pH control of the properties of transition metal complexes containing such ligands.

scholarly journals Interactions between Ultrastable Na4Ag44(SR)30 Nanoclusters and Coordinating Solvents: Uncovering the Atomic-scale Mechanism

2020 ◽  
Author(s):  
Daniel M. Chevrier ◽  
Brian E. Conn ◽  
Bo Li ◽  
De-En Jiang ◽  
Terry P. Bigioni ◽  
...  
Keyword(s):  
Theoretical Calculations ◽  
Atomic Scale ◽  
Water Molecules ◽  
X Ray ◽  
Silver Nanocluster ◽  
Ligand Interactions ◽  
Surface Metal ◽  
Solvent Molecules ◽  
Aqueous Conditions ◽  
Metal Ligand

We report the mechanism on the ultrahigh stability of Na<sub>4</sub>Ag<sub>44</sub>(SR)<sub>30</sub> by uncovering how coordinating solvents interact with the Na<sub>4</sub>Ag<sub>44</sub>(SR)<sub>30</sub> nanocluster at the atomic scale. Through synchrotron X-ray experiments and theoretical calculations, it was found that strongly coordinating aprotic solvents interact with surface Ag atoms, particularly between ligand bundles, which compresses the Ag core and relaxes surface metal-ligand interactions. Furthermore, water was used as a cosolvent to demonstrate that semi-aqueous conditions play an important role in protecting exposed surface regions and can further influence the local structure of the silver nanocluster itself. Notably, under semi-aqueous conditions, aprotic coordinating solvent molecules preferentially remain on the metal surface while water molecules interact with ligands, and ligand bundling persisted across the varied solvation conditions.

scholarly journals Interactions between Ultrastable Na4Ag44(SR)30 Nanoclusters and Coordinating Solvents: Uncovering the Atomic-scale Mechanism

2020 ◽  
Author(s):  
Daniel M. Chevrier ◽  
Brian E. Conn ◽  
Bo Li ◽  
De-En Jiang ◽  
Terry P. Bigioni ◽  
...  
Keyword(s):  
Theoretical Calculations ◽  
Atomic Scale ◽  
Water Molecules ◽  
X Ray ◽  
Silver Nanocluster ◽  
Ligand Interactions ◽  
Surface Metal ◽  
Solvent Molecules ◽  
Aqueous Conditions ◽  
Metal Ligand

We report the mechanism on the ultrahigh stability of Na<sub>4</sub>Ag<sub>44</sub>(SR)<sub>30</sub> by uncovering how coordinating solvents interact with the Na<sub>4</sub>Ag<sub>44</sub>(SR)<sub>30</sub> nanocluster at the atomic scale. Through synchrotron X-ray experiments and theoretical calculations, it was found that strongly coordinating aprotic solvents interact with surface Ag atoms, particularly between ligand bundles, which compresses the Ag core and relaxes surface metal-ligand interactions. Furthermore, water was used as a cosolvent to demonstrate that semi-aqueous conditions play an important role in protecting exposed surface regions and can further influence the local structure of the silver nanocluster itself. Notably, under semi-aqueous conditions, aprotic coordinating solvent molecules preferentially remain on the metal surface while water molecules interact with ligands, and ligand bundling persisted across the varied solvation conditions.

scholarly journals Metal–ligand interactions in complexes of cyclen-based ligands with Bi and Ac

2021 ◽  
Author(s):  
Attila Kovács ◽  
Zoltán Varga
Keyword(s):  
Basis Sets ◽  
Ring Size ◽  
Complex Stability ◽  
Chelating Ligands ◽  
Ligand Interactions ◽  
Bonding Properties ◽  
State Method ◽  
Targeting Vector ◽  
Pendant Arms ◽  
Metal Ligand

AbstractThe structural and bonding properties of Bi and Ac complexes with cyclen-based chelating ligands have been studied using relativistic DFT calculations in conjunction with TZ2P all-electron basis sets. Besides the parent cyclen ligand, the study has covered its extensions with pyridine-type (Lpy), carboxylate (DOTA, DOTPA), picolinate (MeDO2PA) and phosphonate (DOTMP) pendant arms. The effect of the cyclen ring size has been probed by increasing it from [12]aneN4 to [16]aneN4. Additional extensions in the DOTA complexes included the H2O ligand at the 9th coordination site as well as the p-SCN-Bn substituent (a popular linker to the targeting vector). The study focuses on the complex stability, the nature of bonding and the differences between Ac and Bi in the complexes. The metal–ligand interactions have been analysed by the Extended Transition State method combined with Natural Orbitals of Chemical Valence theory and Quantum Theory of Atoms in Molecules models.

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